Antioxidant



20 -For example, the following compounds are position ispreparedcontaining blended planta Patented May 7,1935 j, y 2,000,044

' i UNITED STATES. PATENT OFFICE.

Goodrich Company, New York, N. Y., a I c'orporationof New YorkAPPlicafionMar 26, 1933, '7 Serial No. 673,114 r a V .c a. 4 {29 Claims.c1.1s-'-so') g r a This invention relates to-theart' of preserving whileanother portion is further mixed with 0.96

rubber, fatty oils, petroleum products; synthetic parts by weight (0.5%of the. composition): of plasticsand like organic materials againstunduly tetramethyl p,pf diamino diphenyl carbinol, com rapiddeterioration due to'oxidatijon {and the likegjmonly. known astetramethyl diamino bomb 1 This'invention; infbrief; consists intreating drol. 7 After 1 vulcanization in a press for 45' 5 the rubberor other organic material-with a minutes at 294 F. to produce an optimumcure, member of a class of compo mds' which maybe it is found that thecomposition containing the designated as amino-substituted" poly-arylcarantioxidant deteriorates only approximately binols, or specificallyas jamino substituted one-half as fast as the controlcomposition when 1obenzhydrols 'Ihey'have the generalstructural subjected to an acceleratedaging test suchas 1o formula" the 'GBEI oven test.

X v :It isv to be understood that the term treat: R'= 7 ing is employedin therappended claims in a x --0 generic sense to include either theincorporation where A represents a" primary, secondary, or tertiaryamino group, R'represents an aromatic nucleus, R represents an arylradical which may and preferably-does containan amino group, and Xrepresents H or a hydrocarbon group;

by mixing them into the said material while it is in a plasticor fluidcondition,,or by applyma them to the surface of a-solid mass thereof asa paste, powderv or solution. 7 The term rubber is likewise employed inthe claims in a generic senseto includecaoutchouc both natural and-5'synthetic, balata, guttapercha, rubber isomers phenylaminodiphenylcarbinol; p-dimenthylamlike produc rw et l not a d K mphenylrcarbmol; i diaminowdiphenyl' fillers, pigments, or --vulcan1zmg oracceleratingcarbinol; p, p diamino 0,0 ditolyl carbinol; dia V I '25diamino WhileIhave herein d sclosed certain preferred amino dinaphthylcarbin a phenyl methyl carmnon p,p' diamino trimanners 0i performmg mymvenileni 1 m phenyl carbinol;jp',p' ditmethylamino) diphenyl therebydame p -m m solely carbinol; p,p di(ethylamino diphenyl carbinol;mgretoi mthertq t d h preclse 3 portions of the materials utilized maybe varied (benzylamino) diphenylcarbinol; p,'p di(pheny1- and mmaterials having Q lQ amino) diphenyl carbinol; p,p di(p--tolyl-Properties m be g f d sea d fh? ammd) diphenyl carbinol; ",di( 5departing from the spiritzand scope of the illamino) diphenyl carbinol;p u n vention as defined in the ap ended claims. triphenyl carbinol;'tetramethyl p, p' dia'mino di- 7 a i a g phenyl carbinol; p,pgdiQhenyl-ethylamino) i p d g application $611121 diphenyl carbinol;tetramethyl p,p diamino trifi d'Al1g'i1'St'22, '192'8. phenyl carbinol;tetrametliyl diamino dinaph- 'I claim:

thyl carbinol; p,p', p" triamino triphenyl car- 1. The method ofretarding the deterioration typical members-of theiclassxof antioxidants described above: p amino diphenyl carbinol; p-

of the anti-oxidantsinto the rubber :or; the like 15 applicationris acontinuation in part "of" 5 so binol; and triphenyl triamino triphenylcarbinol; of rubber which comprises treating rubber with 40 as well asthe corresponding compounds containa poly-aryl carbinol containing atleast onenand ingthe substituent group in the ortho, meta, or not morethan two a mino-groups.

7 other positions. Any vof the above enumerated V 2. The methodofretarding theideterioration compounds, may se i o efieci to of rubberwhich comprises treating rubber withh iq io jvi m W f O -like a diamifiodiar'yl carbinol.

.1 a s eenq is r P r i qd y V SL'The process offincrea'singtheresistance-of,

P emiums say 39 01 135 e fi f rubber to deterioration which comprisesincorexaimple 9 p n f? 'porating with the rubber apr'oduct having the Vthe invention of this appl1cat1on,a rubber comfollowing general formulag 7 tion rubber parts by weight sulphur 5.5 g t U B parts, zinc oxide 30parts, gas black 40jparts, 1 n =& /V mineral rubber 10parts, palm oil 5parts, and a 7 S hexaznethylene tetramine'o 'is parts. Onep'or r v g oftfon of thiscomposition is used as a control wherein A and A representamino iroupscr 66 7 to" r of mixing with the unvulcanized rubber 4. Theprocess of increasing the resistance of 7 rubber to deterioration whichcomprises incorporating with the rubber tetra-methyl-diaminobenzhydrol.

, 5. In'the art'of'vulcanizing rubber, the step of mixing-with thelunvulcanized rubber a vulcanizing agent and a compound having thegeneral formula 1 wherein A and A representamino groups or monoordialkyl amino groups, and R and'R represent arylene nuclei, izing. I V6; In the art'of vulcanizing rubber, the step of mixing with theunvulcanized rubber a vulcaniz: ingagent and a compound having] theformula set forth in claim 3, in which formula at least one of A and Arepresent an alkyl'substituted amino group,=and thereafter vulcanizing.V l

7. In the art of vulcanizing rubber, the step of mixing with theunvulcanized rubber a vulcani'zing'agent and a compound having the for-'mula set forth in claim 3, in which formulaat least one of A and Arepresents a dialkyl substituted amino group, and thereaftervulcanizingr I a t r e 8. In the art of vulcanizing rubber, the step ofmixing-with theunvulcanizedrubber a vulcanizing agent and acompoundhaving the formula set forth in'claim 3, in which formula both A and Arepresent an alkyl-substituted amino group, and thereafter 'vulcanizing.t

'9'. "In theart of vulcanizing rubber, the step of'inixing with theunvulcanizedrubber a vulcanizing agent and, a compound having theformulaset 'forthin-claim 3, in which formula both A and-Arepresenta-dialkyl substituted amino group, and thereafter vulcanizing. 10. Inthe art of 'vulcanizing-rubber, the-step a vulcanizing agent and acompound having a formulaset forth in claim 3, in-which formula both Rand R represent phenyl radicals, and there- 'aftervulcanizing. V f"l1;'I n the art of vulcanizing rubber, the step of mixing with the;unvulcanized rubbera vulcanizing agent anda 'compoun'dhaving the formulaset'forth in claim 3, in which formula both A and A represent alkylsubstitutedamino groups, and both R and R represent phenyl groups, andthereafter vulcanizing.

'f"12.'fIn' the' art of 'vulcanizing rubber, the step ofrnixing'with theunvulcanized rubber a vulcanizin'g agentand tetra-methyl-diamino-benzhrd iv nd l rf d g ffru n z L 1 13. .The I method of preserving rubberwhich comprises treatingrubber with a compound hav ing the generalformula II AB A' 4 wherein R and R" represent arillenegroups, A and Arepresent amino groups and X represents a carbinol group, andjin whichany of the groups may contain hydrocarbon substituents, butn ot e htuent A 3 14:The method"of preserving rubber which h e t and t f at 6}:vukan represents a carbmol group, and A and A reprecomprises treatingrubber with a compound havingthe general formula wherein R and Rrepresent aromatic hydrocarbon nuclei selected from the benzene series,A and A represent amino groups, and X represents a carbinol group, andinwhich at least one of the groups A, A and X contains a hydrocarbonsubstituent, but which contains no other substituents.

15. The method of preserving rubber which comprises treating rubber witha substance having the general formula, r

.A X wherein R and'R represent aromatic nuclei, X

sent arylamino groups. p g- T 16. The ,method of preserving rubber which'comprises'trea'ting rubber with p, p di( naphthylamino) .diphenyl carbi'nol. 17. A "composition comprising rubber and poly-arylfcarbinolcontaining: at least one and not more'than two amino groups.

18. A composition, comprising rubber and a diamino diaryl carbinol. i Cv I9. Rubber having incorporated therewith an a'riti aging compoundhaving the general formula o wherein both A and A represent an alkylsubstituted amino group, and R and R represent arylene'radicals,andthereafter vulcanizing. V

, 2 2. Vulcanizedrubber obtained by incorporating therewith avulcanizing agent and an antiaging compound having the general formula.

wherein both A and A'- represent a-dialkylsubstituted amino group,:and Rand R represent phenylene radicals, and thereafter vulcanizing. 23.--Vulcanized rubber obtained by incorporating with the rubber priorto'vulcanization from 1 to' 5% of" tetra-methyl-diamino-benzhydrol andiavulcanizing agent, and thereafter vulcan- '24, Inrthe art ofvulcanizin'g rubber, the step of mixing with the unvulcanized rubber a'vu1-' canizing agent and p, p-diamino-benzhydrol, and thereafterjvulcanizing. j 25.- Vulcanized, rubber obtained by in'corporat ingwiththe rubber prior to vulcanizing from 1 'to'5'% 'of'p,p-diamino-benzhydro1."

26. A composition comprising rubber and a compound having the generalformula wherein R and R represent arylene groups, A and A representamino groups and X represents a carbinol group, and in which any of thegroups may contain hydrocarbon substituents, but no other substituents.

27. A composition comprising rubber and a compound having the generalformula wherein R and R represent aromatic hydrocarbon nuclei selectedfrom the benzene series, A

and A represent amino groups, and X represents a carbinol group, and inwhich at least one of the groups A, A and X contains a hydrocarbonsubstituent,-but which contains no other substituents.

28. A composition comprising rubber and a substance having the generalformula ARX--R'.-A

wherein R and R represent aromatic nuclei, X

represents a carbinol group, and A and A rep resent arylamino groups.

29. A composition comprising rubber and p, p

di(n aphthylamino) diphenyl carbinol.

ARTHUR W. SLOAN.

